Derivatives of polymers for permanent modification of hydrophobic polymers

ABSTRACT

The present invention relates to polymer compositions comprising at least one hydrophobic polymer and at least one modified polyisobutene; fibers, films, moldings and their further processing products formed from this polymer composition, a process for producing the polymer composition according to the present invention, a process for producing the fibers, films and moldings formed from the polymer composition according to the present invention; dyed polymer compositions comprising at least one hydrophobic polymer, at least one modified polyisobutene and at least one dye; and also fibers, films and moldings formed from the dyed polymer composition according to the present invention and the use of modified polyisobutenes for treating hydrophobic polymers.

The present invention relates to polymer compositions comprising atleast one hydrophobic polymer and at least one modified polyisobutene;fibers, films, moldings and their further processing products formedfrom this polymer composition, a process for producing the polymercomposition according to the present invention, a process for producingthe fibers, films and moldings formed from the polymer compositionaccording to the present invention; dyed polymer compositions comprisingat least one hydrophobic polymer, at least one modified polyisobuteneand at least one dye; and also fibers, films and moldings formed fromthe dyed polymer composition according to the present invention and theuse of modified polyisobutenes for treating hydrophobic polymers.

Hydrophobic polymers, especially polyolefins, have numerous excellentproperties such as low specific density, high breaking strength, goodresistance to chemicals, low wettability by polar media such as waterand alcohols, low water imbibition and attendant rapid drying and a lowtendency to rot as well as low cost. They are readily processible intovarious forms such as fibers, films and moldings. The low wettability bypolar substances and the low absorbability by these substances have adisadvantageous effect, however. Thus, hydrophobic polymers, especiallypolyolefins, and fibers, films and moldings formed therefrom are verydifficult if not impossible to dye from aqueous baths, very difficult orimpossible to coat or print and difficult to adhere to other materials.Coatings with polar materials, for example polymers or metals, have pooradhesion to a hydrophobic polymer surface.

These deficiencies are obstacles to an even wider use of hydrophobicpolymers, especially polyolefins. For instance, despite their favorableproperties, polypropylene fibers are rarely used as apparel fibers,specifically in the sports or outdoor apparel sector. To remedy thesedisadvantages of hydrophobic polymers, especially of polyolefins,numerous processes have been proposed for hydrophilicizing them as aprecondition for dyeability, printability, coatability or adherability.

It is customary for hydrophobic polymer fibers to be solution dyed toobtain deep shades, ie for the color pigment to be added in the extruderin the course of the yarn production process. True, this gives dark andfast colorations, but only the production of large solution-dyed batchesis commercially sensible, so that no fashion-based color requirementscan be entertained. Nor is it possible to achieve brilliant shades.Finally, solution dyeing gives rise to large amounts of waste with anychange in color.

Several fundamentally different methods are in existence forhydrophilicizing and hence for improving especially the dyeability ofhydrophobic polymers, especially polyolefins, from aqueous dyebaths.

WO 93/06177 relates to the use of swelling agents to dye polymericfibers which have a limited number of dye sites, especially polyolefinfibers, with disperse dyes. However, this approach, which is known ascarrier dyeing in the case of polyester, entails human-toxicological andenvironmental problems due to the residues remaining in the textile.

Melliand Textilberichte 77 (1996) 588-592 and 78 (1997) 604-605 relatesto the dyeing of polypropylene fibers with specific ultrahydrophobicdisperse dyes under high temperature conditions, preferably in theadditional presence of selected surfactants in the dyeing liquor, toincrease the fixation yields and to obtain dyeings of high levelness.The problem here is that dyers and finishers would have to maintain anadditional stock of dyes exclusively for polyolefin dyeing, and thiswould be very costly.

DE-A 2 210 878 relates to the dyeing of untreated polyolefin fibers withmetal complex dyes. The metals used are chromium, copper, iron, cobalt,nickel, zinc or aluminum. The disadvantage with this process is thatsmall amounts of the heavy metals used end up on the skin when thus dyedtextiles are worn and may cause harmful effects.

There have also been numerous publications relating to a modification ofthe hydrophobic polyolefins, especially in order that improveddyeability may be achieved for polyolefin fibers.

JP-A 7032394, JP-A 6902090, JP-A 6921196 and JP-A 6931810 each relate tothe incorporation of metal complexes into the polymer matrix duringfiber production. These metal complexes can then lock the dye into thefiber interior. One disadvantage with this process is again that smallamounts of the metals used (among those mentioned are nickel, zinc,chromium, copper, cobalt and aluminum) end up on the skin when thus dyedtextiles are worn and may cause harmful effects.

EP-A 0 039 207 relates to modifying the polyolefin fiber byincorporating nitrogenous basic copolymers into the spinning melt of thepolyolefin material. This locks these basic copolymers into themacromolecule. These modified polyolefins then have an affinity foranionic dyes.

V. Flaris, Annual Techn. Conf. Soc. Plastic Engineers 2000, 2826-2830relates to dyeable polypropylene fibers which have been modified bymixing with a reaction product of maleate polypropylene with apolyetheramine. However, the modified polymer has a yellowishdiscoloration and the modifying reaction product has to be used in suchlarge amounts that the fiber properties of the polypropylene, forexample its breaking strength, are impaired.

DE-A 2 240 534 relates to dyeable polyolefin-based compositions whichinclude a polyamine adduct which has at least one hydrocarbyl chain ofat least 25 carbon atoms which is attached to a nitrogen atom. Theadditives are incorporated into the composition by mixing with thepolyolefin. Disadvantages with this process are the large amounts ofadditives needed to achieve dyeability (at least 3% by weight andpreferably 5-15% by weight, based on the composition) and the fact thatthese additives are obtained from chlorinated polyisobutenes.

Polyolefins may further be modified by grafting.

WO 96/26308 relates to the grafting of polyolefins with polar monomers,for example dialkylamino methacrylates, that are able to enter bondswith dyes. The substrate is impregnated with the polar monomer and aninitiator and reacted therewith by heating. This process is thus verycostly and inconvenient and requires the handling of monomers which maybe harmful.

U.S. Pat. No. 3,807,951 relates to grafted polyolefins which have beengrafted with nitrogen-containing monomers such as N-vinylpyridine,N-vinylpyrrolidone or dialkylamino methacrylates. The graft polymer issubsequently quaternized to render it dyeable with anionic dyes. Onedisadvantage with this process is that it is very complicated to carryout and hence very costly. Furthermore, the free-radical initiators usedin the grafting often cause substantial shortening of the polymer chainsof the polyolefin, so that its performance properties are impaired.

WO 94/09067 relates to mixtures of functionalized and unfunctionalizedpolyolefins. The functionalization of the polyolefins is accomplished byreaction with a carboxylic anhydride, preferably maleic anhydride. Thisconfers improved affinity for polar materials, improved dyeability andprintability on polyolefins. The disadvantage is that a mixing operationhas to be carried out as well as grafting.

It is an object of the present invention to provide hydrophobicpolymers, especially polyolefins, that are modifiable with hydrophilicmaterials which are in particular dyeable, printable, coatable andadherable. The modification of the hydrophobic polymers, especiallypolyolefins, shall be accomplished in a simple process usingenvironmentally friendly and inexpensive substances.

We have found that this object is achieved by a polymer compositioncomprising

-   -   a) at least one hydrophobic polymer, and    -   b) at least one polyisobutene which is modified by terminal        polar groups and is obtainable by functionalization of reactive        polyisobutene having a number average molecular weight M_(n)        from 150 to 50 000.

The polymer compositions according to the present invention are simpleto produce and are effective to hydrophilicize the hydrophobic polymersused, so that the polymer compositions and also further processingproducts of the polymer compositions are dyeable, printable, coatableand adherable without the need to use special dyes, coatings oradhesives.

Component A (Hydrophobic Polymers)

Any hydrophobic polymer is suitable in principle. Polyolefins arepreferred. Any known polyolefin is suitable in principle. Preference isgiven to polyolefins constructed of basic C₂-C₄ structural repeat units.They can be homopolymers or they can be copolymers, in which case thecopolymers can be random copolymers or block copolymers. Ethylene andother α-olefins, dienes or polyenes are suitable comonomers, dependingon the polyolefin's basic structural repeat units. The fraction of thecopolymer that is attributable to comonomers is generally not more than40% by weight, for example 20-30% or 2-10%, depending on theapplication.

The polymer compositions according to the present invention morepreferably comprise homo- or copolymers of propylene or of ethylene.

In a preferred embodiment, the polyolefin used is polyethylene and morepreferably linear polyethylene (HDPE, LLDPE). This can be used in theform of its homopolymer or as a random or block copolymer, in which caseall customary comonomers can be used.

In a further particularly preferred embodiment, the polyolefin used ispolypropylene. The polypropylene in question can be a homopolymer or arandom or block copolymer of propylene.

The random or block polypropylenes can contain up to 40% by weight of acomonomer. Suitable comonomers include for example ethylene orα-olefins, dienes such as 1,4-hexa-diene, 1,5-hexadiene, 1,6-heptadiene,2-methyl-1,4-pentadiene, 1,7-octadiene, 6-methyl-1,5-heptadiene, orpolyenes such as octatriene or dicyclopentadiene.

The polymers can generally be atactic, isotactic or syndiotactic,preference being given to isotactic polymers. The polymers are producedby conventional methods, for example by using Ziegler-Natta ormetallocene catalysts.

Further details will be known to one skilled in the art or can be readup for example in the polyolefins chapter of “Ullmanns Encyclopedia (ofTechnical Chemistry), 6^(th) Edition, 2000 Electronic Release” and thereferences cited therein.

Component B (Modified Polyisobutene)

The modified polyisobutene used as component B is a polyisobutene whichis modified by terminal polar groups and obtainable by functionalizationof polyisobutene having a number average molecular weight M_(n) from 150to 50 000 and containing not less than 60 mol % of terminal double bonds(α- and/or β-olefins) or their precursor.

The modified polyisobutenes can be linear or substantially linearpolyisobutene derivatives which have a polar group only at one chainend. Structures of this kind are known as head-to-tail structures. Theycan further be linear or substantially linear polyisobutene derivativeswhich have polar groups at both chain ends. Furthermore, it is alsopossible to use branched polyisobutene derivatives which contain threeor more chain ends having polar groups. The present invention is notrestricted to a particular branching pattern. Naturally, mixtures ofvarious polyisobutene derivatives can also be used for the polymercompositions according to the present invention.

The modified polyisobutene derivatives are obtainable byfunctionalization of reactive polyisobutene starting material. Reactivepolyisobutene for the purposes of the present invention is polyisobutenehaving reactive groups at one or two or—when branched reactivepolyisobutenes are used—at three or more chain ends.

The reactive groups at the chain ends may in principle be any desiredgroup, provided they can be suitably reacted to give a terminal polargroup. The reactive groups are preferably α- or β-olefin groups and also—C(CH₃)₂-Z groups, which can be reacted directly or followingelimination by way of the olefin stage. In order to be able to achievethe degrees of functionalization specified at the outset, it isnecessary in each case for there to be at least a corresponding amountof reactive chain ends in the unmodified polyisobutylene.Polyisobutylene chains having a nonreactive chain end such as—C(CH₃)═C(CH₃)—CH(CH₃)₂ do not undergo polar modification, areineffective and/or impair the effect. It is therefore preferable forthere to be a relatively large amount of reactive chain ends present.Preferably, the reactive chain ends are formed in a basically knownmanner in the course of the termination of the polymerization, althoughit is also possible—albeit not preferable—for the chain ends to beprovided with reactive groups in a separate reaction step. The reactivepolyisobutene more preferably contains not less than 50 mol %,preferably not less than 60 mol % and more preferably not less than 80mol % of terminal double bonds. Terminal double bonds of polyisobutenerefers to double bonds in the α- or β-position of the polyisobutene.

The reactive polyisobutene for the purposes of this invention preferablyrefers to a polyisobutene which in total contains not less than 60% ofunits derived from vinyl isomer (β-olefin, R—CH═C(CH₃)₂) and/orvinylidene isomer (α-olefin, R—C(CH₃)═CH₂) or appropriate precursorssuch as R—C(CH₃)₂Cl.

The polyisobutenes used according to the present invention have a numberaverage molecular weight M_(n) from 150 to 50 000, preferably from 200to 35 000 and more preferably from 300 to 6000, for example about 550,about 1000 or about 2300. The molecular weight distribution of thepolyisobutenes used according to the present invention is generallynarrow. The molecular weight distribution (M_(w)/M_(n)) is preferably inthe range from 1.05 to 4 and more preferably in the range from 2 to 3.If desired, however, it is also possible to use polyisobutenes having abroader molecular weight distribution of for example >5 or even >12.

Suitable reactive polyisobutenes are obtainable for example by cationicpolymerization of isobutene.

Suitable starting materials are preferably synthesized using isobutenealone. However, cationically polymerizable comonomers may also be usedas well. The amount of comonomers, however, should generally be lessthan 20% by weight, preferably less than 10% by weight and morepreferably less than 5% by weight.

Suitable comonomers include in particular styrenics such as styrene andα-methylstyrene, C₁-C₄-alkylstyrenes such as 2-, 3- and 4-methylstyrene,and also 4-tert-butylstyrene, C₃- to C₆-alkenes such as n-butene,isoolefins having from 5 to 10 carbon atoms such as2-methylbutene-1,2-methylpentene-1,2-methylhexene-1,2-ethylpentene-1,2-ethylhexene-1and 2-propylheptene-1.

Isobutene feedstocks suitable for synthesizing the starting materialinclude not only isobutene itself but also isobutene-containing C₄hydrocarbon streams, for example C₄ raffinates, C₄ cuts from isobutenedehydrogenation, C₄ cuts from steam crackers or fluid catalyzed cracking(FCC) crackers, provided they have been substantially freed of1,3-butadienepresent therein. C₄ hydrocarbon streams suitable accordingto the present invention generally contain less than 500 ppm andpreferably less than 200 ppm of butadiene. The presence of butene-1,cis-butene-2 and trans-butene-2 is substantially uncritical for theprocess of the present invention and does not lead to selectivitylosses. The concentration in the C₄ hydrocarbon streams is typically inthe range from 40% to 60% by weight. When C₄ cuts are used as afeedstock, the hydrocarbons other than isobutene perform the function ofan inert solvent.

The reaction may be catalyzed with BF₃ alone, BF₃ complexes withelectron donors or mixtures thereof. Electron donors (Lewis bases) arecompounds which have a free electron pair, on an oxygen, nitrogen,phosphorus or sulfur atom for example, and are able to form complexeswith Lewis acids. This complexing is desirable in many cases, since itreduces the activity of the Lewis acid and suppresses side reactions.Examples of suitable electron donors are ethers such as diisopropylether or tetrahydrofuran, amines such as triethylamine, amides such asdimethylacetamide, alcohols such as methanol, ethanol, i-propanol ort-butanol. The alcohols additionally act as a source of protons and soinitiate the polymerization. A cationic polymerization mechanism mayalso be activated via protons from ubiquitous traces of water.

Suitable solvents for the polymerization include all organic compoundswhich are liquid in the selected temperature range and which neitherdetach protons nor possess free electron pairs. These include inparticular cyclic and acyclic alkanes such as ethane, isopropane,n-propane, n-butane and its isomers, cyclopentane and also n-pentane andits isomers, cyclohexane and also n-hexane and its isomers, n-heptaneand its isomers and also higher homologs, cyclic and acyclic alkenessuch as ethene, isopropene, n-propene, n-butene, cyclopentene and alson-pentene, cyclohexene and also n-hexene, n-heptene, aromatichydrocarbons such as benzene, toluene or the isomeric xylenes. Thehydrocarbons may also be halogenated. Examples of halogenatedhydrocarbons include methyl chloride, methyl bromide, methylenechloride, methylene bromide, ethyl chloride, ethyl bromide,1,2-dichloroethane, 1,1,1-trichloroethane, chloroform and chlorobenzene.Mixtures of the solvents can also be used, provided no undesirableproperties occur.

From an engineering standpoint it is particularly advisable to usesolvents which boil in the desired temperature range. The polymerizationtypically takes place at from −80° C. to 0° C., preferably from −50° C.to −5° C. and more preferably at from −30° C. to −15° C.

Cationic polymerization under BF₃ catalysis produces substantiallylinear polyisobutenes which have a particularly high α-olefin groupcontent at one chain end. With a suitable reaction regime, the α-olefincontent will not be less than 80%.

Reactive polyisobutenes which have reactive α-olefin groups at bothchain ends or which are branched may be obtained in a particularlyelegant fashion by means of living cationic polymerization. Obviously,linear polyisobutenes which have an α-olefin group only at one chain endmay also be synthesized by this method, however.

In a living cationic polymerization, isobutene is polymerized with asuitable combination of an initiator molecule IX_(n) with a Lewis acidS. Details of this method of polymerization are disclosed for example inKennedy and Ivan, “Carbocationic Macromolecular Engineering”, HanserPublishers 1992.

Suitable initiator molecules IX_(n) have one or more leaving groups X.The leaving group X is a Lewis base, which may be further substituted.Examples of suitable leaving groups include the halogens fluorine,chlorine, bromine and iodine, straight-chain and branched alkoxy groups,such as C₂H₅O—, n-C₃H₇O—, i-C₃H₇O—, n-C₄H₉O—, i-C₄H₉O—, sec-C₄H₉O— ort-C₄H₉O—, and also straight-chain and branched carboxyl groups such asCH₃CO—O—, C₂H₅CO—O—, n-C₃H₇CO—O—, i-C₃H₇CO—O—, n-C₄H₉CO—O—, i-C₄H₉CO—O—,sec-C₄H₉CO—O—, t-C₄H₉CO—O—. Connected to the leaving group or groups isthe moiety I, which is able to form carbocations I⁺ which aresufficiently stable under reaction conditions. To initiate thepolymerization, the leaving group is abstracted by means of a suitableLewis acid S: I−X+S-->I⁺+XS⁻ (shown here only for n=1). The resultingcarbocation I⁺ initiates the cationic polymerization and is incorporatedinto the resulting polymer. Examples of suitable Lewis acids S includeAlY₃, TiY₄, BY₃, SnY₄, ZnY₂ where Y is fluorine, chlorine, bromine oriodine. The polymerization reaction can be terminated by destroying theLewis acid, for example by reacting it with an alcohol. This producespolyisobutene which possesses the terminal-C(CH₃)₂-Z groups, which cansubsequently be converted into α- and β-olefin end groups.

Preferred initiator molecules are structures which are capable offorming tertiary carbocations. Particular preference is given toradicals which derive from the lower oligomers of isobutene,H—[CH₂—C(CH₃)₂]_(n)—X, where n is preferably from 2 to 5. Linearreactive polyisobutenes formed using such initiator molecules have areactive group at one end only.

Linear polyisobutenes which have reactive groups at both ends areobtainable using initiator molecules IXQ which have two leaving groups Xand Q, which may be the same or different. Compounds which contain—C(CH₃)₂—X groups are established in the art. Examples includestraight-chain or branched alkylene radicals C_(n)H_(2n) (where n ispreferably from 4 to 30), which may be interrupted by a double bond orby an aromatic moiety, such as

X—(CH₃)₂C—CH₂—C(CH₃)₂-Q, X—(CH₃)₂C—CH₂—C(CH₃)₂CH₂—C(CH₃)₂-Q,

X—(CH₃)₂C—CH₂—C(CH₃)₂CH₂—C(CH₃)₂CH₂—C(CH₃)₂-Q or

X—(CH₃)₂C—CH₂—C(CH₃)₂CH₂—C(CH₃)₂CH₂—C(CH₃)₂—CH₂—C(CH₃)₂-Q,

X—(CH₃)₂C—CH═CH—C(CH₃)₂-Q or para and/or meta

X—(CH₃)₂C—C₆H₄—C(CH₃)₂-Q.

Branched polyisobutenes are obtainable using initiator molecules IX_(n)which have 3 or more leaving groups, which may be the same or different.Examples of suitable initiator molecules includeX—(CH₃)₂C—C₆H₃—[C(CH₃)₂-Q]-C(CH₃)₂—P as 1,2,4 and/or 1,3,5 isomer, theleaving groups preferably being the same, but they can also bedifferent. Further examples of mono-, di-, tri- or polyfunctionalinitiator molecules can be found in the Kennedy and Ivan paper which wascited at the outset and also in the references cited therein.

The reactive polyisobutenes are reacted with suitable reagents to givethe desired polyisobutene derivatives having terminal polar groups.

The degree of functionalization of the modified polyisobutenederivatives having terminal polar groups is not less than 65%,preferably not less than 75% and most preferably not less than 85%. Inthe case of the polymers having polar groups at one chain end only, thisfigure refers only to said one chain end. In the case of the polymershaving polar groups at both chain ends, and also in the case of thebranched products, this figure refers to the total number of all chainends. The unfunctionalized chain ends comprise both those which do nothave a reactive group at all and those in which a reactive group,although present, was not converted in the course of thefunctionalization reaction.

The term “polar group” is known to one skilled in the art. The polargroups may be protic as well as aprotic polar groups. The modifiedpolyisobutenes thus have a hydrophobic moiety comprising a polyisobuteneradical and also a moiety, having a certain hydrophilic character atleast to some extent, comprising terminal polar groups. The groups inquestion are preferably strongly hydrophilic groups. The terms“hydrophilic” and “hydrophobic” are known to one skilled in the art.

Polar groups include for example sulfonic acid radicals, anhydrides,carboxyl groups, carboxamides, OH groups, polyoxyalkylene groups, aminogroups, epoxides or suitable silanes which may be suitably substituted.

Suitable reactions for introducing polar groups (functionalization) areknown in principle to one skilled in the art.

In principle, the functionalization of the polyisobutenes used accordingto the present invention can be carried out in one or more stages.

In a preferred embodiment, the functionalization of the polyisobuteneused according to the invention is accomplished in one or more stagesand is selected from:

-   -   i) reaction with aromatic hydroxy compounds in the presence of        an alkylation catalyst to obtain polyisobutene-alkylated        aromatic hydroxy compounds,    -   ii) reaction of the polyisobutene with a peroxy compound to        obtain an epoxidized polyisobutene,    -   iii) reaction of the polyisobutene with an alkene having an        electrophilically substituted double bond (an enophile) in an        ene reaction,    -   iv) reaction of the polyisobutene with carbon monoxide and        hydrogen in the presence of a hydroformylation catalyst to        obtain a hydroformylated polyisobutene,    -   v) reaction of the polyisobutene with hydrogen sulfide or a        thiol to obtain a thio-functionalized polyisobutene,    -   vi) reaction of the polyisobutene with a silane in the presence        of a silylation catalyst to obtain a silyl-functionalized        polyisobutene,    -   vii) reaction of the polyisobutene with halogen or a hydrogen        halide to obtain a halogen-functionalized polyisobutene,    -   viii) reaction of the polyisobutene with a borane and subsequent        oxidative cleavage to obtain a hydroxylated polyisobutene,    -   ix) reaction of the polyisobutene with an SO₃ source, preferably        acetyl sulfate, to obtain a polyisobutene having terminal        sulfonic acid groups,    -   x) reaction of the polyisobutene with nitrogen oxides and        subsequent hydrogenation to obtain a polyisobutene having        terminal amino groups.        Re i): Alkylation of Aromatic Hydroxy Compounds

The reactive polyisobutene may be derivatized by reaction with anaromatic hydroxy compound in the presence of an alkylation catalyst.Suitable catalysts and reaction conditions for this Friedel-Craftsalkylation are described for example in J. March, Advanced OrganicChemistry, 4th edition, John Wiley & Sons, pages 534-539, incorporatedherein by reference.

The aromatic hydroxy compound used for alkylation is preferably selectedfrom phenolic compounds having 1, 2 or 3 OH groups, which may optionallycontain at least one further substituent. Preferred further substituentsare C₁-C₈-alkyl groups and especially methyl and ethyl. Preference isgiven in particular to compounds of the general formula

where R¹ and R² are independently hydrogen, OH or CH₃. Particularpreference is given to phenol, the cresol isomers, catechol, resorcinol,pyrogallol, fluoroglucinol and the xylenol isomers. Phenol, o-cresol andp-cresol are used in particular. If desired, it is also possible to usemixtures of the aforementioned compounds for alkylation.

The catalyst is preferably selected from Lewis-acid alkylationcatalysts, which for the purposes of the present invention comprehendsnot only individual acceptor atoms but also acceptor-ligand complexes,molecules, etc, provided these have net Lewis acid (electron acceptor)properties. This includes for example AlCl₃, AlBr₃, BF₃, BF₃2 C₆H₅OH,BF₃[O(C₂H₅)₂]₂, TiCl₄, SnCl₄, AlC₂H₅Cl₂, FeCl₃, SbCl₅ and SbF₅. Thesealkylation catalysts can be used together with a cocatalyst, for examplean ether. Suitable ethers are di-(C₁-C₈-)alkyl ethers, such as dimethylether, diethyl ether, di-n-propyl ether, and also tetrahydrofuran,di-(C₅-C₈-)cycloalkyl ethers, such as dicyclohexyl ether and ethershaving at least one aromatic hydrocarbyl, such as anisole. When acatalyst-cocatalyst complex is used for Friedel-Crafts alkylation, themolar ratio of catalyst to cocatalyst is preferably in the range from1:10 to 10:1. The reaction can also be catalyzed with protic acids suchas sulfuric acid, phosphoric acid and trifluoromethanesulfonic acid.Organic protic acids can be present in polymer-bound form, for exampleas ion exchange resin.

The alkylation can be carried out with or without a solvent. Examples ofsuitable solvents are n-alkanes and mixtures thereof and alkylaromatics,such as toluene, ethylbenzene and xylene and also halogenatedderivatives thereof.

The alkylation is preferably carried out from −10° C. to +100° C. Thereaction is customarily carried out at atmospheric pressure, but canalso be carried out at superatmospheric or reduced pressure.

The fraction of alkylated products which is obtained and their degree ofalkylation can be controlled through suitable choice of the molar ratiosof aromatic hydroxy compound to polyisobutene and of the catalyst. Forinstance, substantially monoalkylated polyiso-butenylphenols aregenerally obtained from an excess of phenol or in the presence of aLewis-acid alkylation catalyst when an ether cocatalyst is used inaddition.

The reaction of polyisobutenes with phenols in the presence of suitablealkylation catalysts is disclosed for example in U.S. Pat. No. 5,300,701and WO 02/26840.

A polyisobutenylphenol obtained in step i) may be further functionalizedby Mannich reaction with at least one aldehyde, for exampleformaldehyde, and at least one amine which has at least one primary orsecondary amine function to obtain a polyisobutene-alkylated andadditionally at least partially aminoalkylated compound. It is alsopossible to use reaction and/or condensation products of aldehyde and/oramine. The preparation of such compounds is described in WO 01/25 293and WO 01/25 294 again, which are each hereby incorporated herein infull by reference.

A polyisobutenylphenol obtained in step i) may further be alkoxylatedwith alkylene oxides, preferably ethylene oxide.

ii) Epoxidation

The reactive polyisobutene may be functionalized by reaction with atleast one peroxy compound to obtain an epoxidized polyisobutene.Suitable epoxidation methods are described in J. March, Advanced OrganicChemistry, 4th edition, John Wiley & Sons, pages 826-829, incorporatedherein by reference. Preferably, the peroxy compound used is at leastone peracid, such as m-chloroperbenzoic acid, performic acid, peraceticacid, trifluoroperactic acid, perbenzoic acid and 3,5-dinitroperbenzoicacid. The peracids may be prepared in situ from the corresponding acidsand H₂O₂ in the presence or absence of mineral acids. Further suitableepoxidizing reagents include for example alkaline hydrogen peroxide,molecular oxygen and alkyl peroxides, such as tert-butyl hydroperoxide.Examples of suitable solvents for the epoxidation are customary apolarsolvents. Particularly suitable solvents are hydrocarbons such astoluene, xylene, hexane and heptane.

The epoxidized polyisobutenes obtained in step ii) may be furtherfunctionalized by reaction with ammonia to obtain polyisobutene aminoalcohols (EP-A 0 476 785).

iii) Ene Reaction

The reactive polyisobutene may further be functionalized by reactionwith at least one alkene which has a nucleophilically substituted doublebond in an ene reaction (see for example DE-A 4 319 672 or H. Mach andP. Rath in “Lubrication Science II” (1999), pages 175-185, fullyincorporated herein by reference). In an ene reaction, an alk-ene havingan allyl-disposed hydrogen atom is reacted with a nucleophilic alkene,the enophile, in a pericyclic reaction comprising a carbon-carbon bondformation, a double bond shift and a hydrogen transfer. In the presentcase, the reactive polyisobutene acts as an ene. Suitable enophiles arecompounds which are used as dienophiles in the Diels-Alder reaction. Thepreferred enophile is maleic anhydride. This produces polyisobutenesfunctionalized with succinic anhydride groups (polyisobutenylsuccinicanhydride, PIBSA), as disclosed in EP-A 0 156 310.

The ene reaction may optionally be carried out in the presence of aLewis acid catalyst. Suitable examples are aluminum chloride andethylaluminum chloride.

The reaction creates a new α-olefin group at the chain end. Apolyisobutene derivatized with succinic anhydride groups, for example,may be further functionalized by subjecting it to a second reactionselected from:

-   -   a) reaction with at least one amine to obtain a polyisobutene        partly or fully functionalized with succinimic and/or        succinamide groups,    -   b) reaction with at least one alcohol to obtain a polyisobutene        functionalized with succinic ester groups,    -   c) reaction with at least one thiol to obtain a polyisobutene        functionalized with succinic thioester groups, and    -   d) reaction with maleic anhydride to obtain a product having two        succinic anhydride groups at the chain end (known as PIBBSA).    -   e) Hydrolysis to obtain a polyisobutene functionalized with        succinic acid groups which may be converted into salts. Suitable        cations in salts are in particular alkali metal cations,        ammonium ions and also alkylammonium ions.        Re a) and b)

The succinic anhydride groups may be reacted with polar reactants suchas alcohols and amines, for example, by way of further derivatization.The suitable polar reactants are preferably primary alcohols ROH,primary amines RNH₂ or secondary amines RR′NH, where R is a linear orbranched saturated hydrocarbyl radical which bears at least onesubstituent selected from the group consisting of OH, NH₂ and NH₃ ⁺ andoptionally one or more CH(O) groups and optionally has nonadjacent —O—and/or —NH— and/or tertiary —N-groups, and R′ has the same meaningsindependently of R. Both carboxylic acid groups of the succinicanhydride may be reacted or else only one carboxylic acid group whilethe other carboxylic acid group is present as a free acid group or as asalt. The above substituents may be further modified, for example byalkoxylation.

Further synthetic variants for derivatizing succinic anhydride groupsare mentioned in the applications bearing the file references DE 101 25158.0 and DE 101 476 50.7.

It is also known to one skilled in the art to convert a succinicanhydride group into a succinimide group under suitable conditions.

iv) Hydroformylation

The reactive polyisobutene may be functionalized by reaction with carbonmonoxide and hydrogen in the presence of a hydroformylation catalyst toform a hydroformylated polyisobutene.

Suitable hydroformylation catalysts are known and preferably comprise acompound or complex of an element of transition group VIII of thePeriodic Table, such as Co, Rh, Ir, Ru, Pd or Pt. To influenceactivity/selectivity, it is preferable to use hydroformylation catalystsmodified by N- or P-containing ligands. Suitable salts of these metalsare for example the hydrides, halides, nitrates, sulfates, oxides,sulfides or the salts with alkyl- or arylcarboxylic acids or alkyl- orarylsulfonic acids. Suitable complexes have ligands which are selectedfor example from halides, amines, carboxylates, acetylacetonate, aryl-or alkylsulfonates, hydride, CO, olefins, dienes, cycloolefins,nitriles, N-containing heterocycles, aromats and hetaromats, ethers,PF₃, phosphols, phosphabenzenes and also mono-, bi- and more highlydentate phosphine, phosphinite, phosphonite, phosphoramidite andphosphite ligands.

In general, the catalysts or catalyst precursors used in each case areconverted under hydroformylation conditions into catalytically activespecies of the general formula H_(x)M_(y)(CO)_(z)L_(q), where M is ametal of transition group VIII, L is a ligand and q, x, y and z areintegers which depend on the valency and nature of the metal and also onthe number of coordination sites occupied by the ligand L.

In a preferred embodiment, the hydroformylation catalysts are preparedin situ in the reactor used for the hydroformylation reaction.

Another preferred embodiment utilizes a carbonyl generator wherebypreviously prepared carbonyl is adsorbed onto, for example, activatedcarbon and only the desorbed carbonyl but not the salt solutions fromwhich the carbonyl is produced is fed to the hydroformylation.

Suitable catalysts include rhodium compounds or complexes, for examplerhodium(III) and rhodium(III) salts, such as rhodium(III) chloride,rhodium(III) nitrate, rhodium(III) sulfate, potassium rhodium sulfate,rhodium(III) or rhodium(III) carboxylate, rhodium(II) and rhodium(III)acetate, rhodium(III) oxide, salts of rhodic(III) acid,trisammonium-hexachlororhodate(III), etc. It is also possible to userhodium complexes, such as rhodium biscarbonylacetylacetonate,acetylacetonatobisethylenerhodium(I), etc.

Useful catalysts further include ruthenium salts or compounds. Suitableruthenium salts are for example ruthenium(III) chloride, ruthenium(IV)oxide, ruthenium(VI) oxide, ruthenium(VIII) oxide, alkali metal salts ofruthenium oxo acids such as K₂RuO₄ or KRuO₄ or complexes such as forexample RuHCl(CO)(PPh₃)₃. It is also possible to use the carbonyls ofruthenium such as dodecacarbonyl triruthenium or octadecacarbonylhexaruthenium or mixed forms in which CO is partly replaced by ligandsof the formula PR₃, such as Ru(CO)₃(PPh₃)₂.

Suitable cobalt compounds are for example cobalt(III) chloride,cobalt(II) sulfate, cobalt(II) carbonate, cobalt(II) nitrate, theiramine or aquo complexes, cobalt carboxylates, such as cobalt formate,cobalt acetate, cobalt ethylhexanoate, cobalt naphthenate and also thecobalt-caprolactamate complex. It is similarly possible to use thecarbonyl complexes of cobalt such as octacarbonyl dicobalt,dodecacarbonyl tetracobalt and hexadecacarbonyl hexacobalt.

The aforementioned compounds and further suitable compounds are known inprinciple and are extensively described in the literature.

Suitable activating agents which can be used for hydroformylationinclude for example Brönsted acids, Lewis acids, such as BF₃, AlCl₃ andZnCl₂, and Lewis bases.

The composition of the synthesis gas used, comprising carbon monoxideand hydrogen, can vary within wide limits. The molar ratio of carbonmonoxide to hydrogen is generally in the range of about 5:95-95:5 andpreferably about 40:60-60:40. The temperature in the hydroformylation isgenerally in the range of about 20-200° C. and preferably about 50-190°C. The reaction is generally carried out at the partial pressure of thereaction gas at the reaction temperature chosen. The pressure isgenerally in the range of about 1-700 bar and preferably in the rangefrom 1 to 300 bar.

The carbonyl number of the hydroformylated polyisobutenes obtaineddepends on the number average molecular weight M_(n). The carbonylnumbers of products having a number average molecular weight M_(n) of 10000 dalton are preferably in the range from 2 to 5.6 mg of KOH/g andespecially in the range from 3.6 to 5.6 mg of KOH/g. Products having anumber average molecular weight M_(n) of 40 000 dalton have carbonylnumbers from 0.5 to 1.4 mg of KOH/g and especially from 0.9 to 1.4 mg ofKOH/g. The carbonyl numbers for products having other molecular weightscan be determined by interpolation or extrapolation.

It is preferable for the predominant portion of the double bonds presentin the medium molecular weight reactive polyisobutene used to beconverted into aldehydes by the hydroformylation. The use of suitablehydroformylation catalysts and/or of an excess of hydrogen in thesynthesis gas used also makes it possible to convert the predominantportion of the ethylenically unsaturated double bonds present in thereactant directly into alcohols (see for example DE-A 100 03 105). Thiscan also be achieved in a two-stage functionalization as per thehereinbelow described reaction step B).

The functionalized polyisobutenes obtained by hydroformylation are veryuseful as intermediates for further processing by functionalization ofsome or all of the aldehyde functions they contain.

A) Oxo Carboxylic Acids

The hydroformylated polyisobutenes obtained in step iv) may be furtherfunctionalized by reaction with an oxidizing agent to obtain apolyisobutene partially or fully functionalized by carboxyl groups.

Aldehydes can be oxidized to carboxylic acids using in general a largenumber of different oxidizing agents and processes which are describedfor example in J. March, Advanced Organic Chemistry, John Wiley & Sons,4th edition, pages 701ff. (1992). These include for example oxidationwith permanganate, chromate, atmospheric oxygen, etc. Oxidation withair/oxygen can be carried out not only catalytically in the presence ofmetal salts but also in the absence of catalysts. Preferred metals arecapable of a valency change, such as Cu, Fe, Co, Mn, etc. The reactiongenerally also succeeds in the absence of a catalyst. In the case of airoxidation, the conversion can readily be controlled via the reactiontime.

In a further embodiment, the oxidizing agent used is an aqueous hydrogenperoxide solution in combination with a carboxylic acid, for exampleacetic acid. The acid number of the resulting polyisobutenes having acarboxyl function depends on the number average molecular weight M_(n).The acid numbers of products having a number average molecular weightM_(n) of 10 000 dalton are preferably in the range from 2 to 5.6 mg ofKOH/g and especially in the range from 3.6 to 5.6 mg of KOH/g. Productshaving a number average molecular weight M_(n) of 40 000 dalton haveacid numbers in the range from 0.5 to 1.4 mg of KOH/g and especially inthe range from 0.9 to 1.4 mg of KOH/g. The acid numbers of productshaving other molecular weights can be determined by interpolation orextrapolation.

B) Oxo Alcohols

In a further suitable embodiment, the hydroformylated polyisobutenesobtained in step iv) can be subjected to a reaction with hydrogen in thepresence of a hydrogenation catalyst to give a polyisobutene which ispartially or fully functionalized by alcohol groups.

Suitable hydrogenation catalysts are generally transition metals such asCr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru, etc, or mixtures thereof that canbe applied to supports such as activated carbon, alumina, kieselguhr,etc to increase the activity and stability. To increase the catalyticactivity, it is possible to use Fe, Co and preferably Ni in the form ofRaney catalysts as a metal sponge having a very large surface area.

The hydrogenation of the oxo aldehydes from step iv) is preferablycarried out at elevated temperatures and elevated pressure, depending onthe activity of the catalyst. Preferably the reaction temperature isabout 80-150° C. and the pressure about 50-350 bar.

The alcohol number of the resulting polyisobutenes having hydroxylgroups depends on the number average molecular weight M_(n). The alcoholnumbers of products having a number average molecular weight M_(n) of 10000 dalton are preferably in the range from 2 to 5.6 mg of KOH/g andespecially in the range from 3.6 to 5.6 mg of KOH/g. Products having anumber average molecular weight M_(n) of 40 000 dalton have alcoholnumbers from 0.5 to 1.4 mg of KOH/g and especially from 0.9 to 1.4 mg ofKOH/g. The alcohol numbers of products having other molecular weightscan be determined by interpolation or extrapolation.

The alcohol-functionalized polyisobutenes can additionally bealkoxylated with alkylene oxides, preferably ethylene oxide.

C) Amine Synthesis

In a further suitable embodiment, the hydroformylated polyisobutenesobtained in step iv) are further functionalized by reaction withhydrogen and ammonia or a primary or secondary amine in the presence ofan amination catalyst to obtain a polyisobutene which is partially orfully functionalized by amine groups.

Suitable amination catalysts are the hydrogenation catalysts describedabove in step B), preferably copper, cobalt or nickel, that can be usedin the form of the Raney metals or on a support. It is also possible touse platinum catalysts.

Amination with ammonia gives aminated polyisobutenes having primaryamino functions. Useful primary and secondary amines for amination arecompounds of the general formulae R—NH₂ and RR′NH, where R and R′ areindependently for example C₁-C₁₀-alkyl, C₆-C₂₀-aryl, C₇-C₂₀-arylalkyl,C₇-C₂₀-alkylaryl or cycloalkyl.

The amine number of the resulting polyisobutenes having amino groupsdepends on the number average molecular weight M_(n). The amine numbersof products having a number average molecular weight M_(n) of 10 000dalton are preferably in the range from 2 to 5.6 mg of KOH/g andespecially in the range from 3.6 to 5.6 mg of KOH/g. Products having anumber average molecular weight M_(n) of 40 000 dalton have aminenumbers from 0.5 to 1.4 mg of KOH/g and especially from 0.9 to 1.4 mg ofKOH/g. The amine numbers of products having other molecular weights canbe determined by interpolation or extrapolation.

v) Addition of Hydrogen Sulfide and Thiols

The reactive polyisobutene may be functionalized by reaction withhydrogen sulfide or thiols, such as alkyl or aryl thiols, hydroxymercaptans, amino mercaptans, thio carboxylic acids or silanethiols, toobtain a polyisobutene functionalized by thio groups.

Suitable hydro-alkylthio additions are described in J. March, AdvancedOrganic Chemistry, 4th edition, John Wiley & Sons, pages 766-767,incorporated herein in full. The reaction can generally be carried outnot only in the absence but also in the presence of initiators and alsoin the presence of electromagnetic radiation. The addition of hydrogensulfide gives polyisobutenes functionalized by thiol groups. Thereaction with thiols in the absence of initiators generally gives theMarkovnikov addition products onto the double bond. Suitable initiatorsfor the hydro-alkylthio addition are for example protic and Lewis acids,such as concentrated sulfuric acid or AlCl₃. Useful initiators furtherinclude initiators which are capable of forming free radicals.Hydro-alkylthio addition in the presence of these initiators generallygives the anti-Markovnikov addition products. The reaction can also becarried out in the presence of electromagnetic radiation having awavelength in the range from 10 to 400 nm and preferably in the rangefrom 200 to 300 nm.

vi) Silylation

The reactive polyisobutene may be functionalized by reaction with asilane in the presence of a silylation catalyst to obtain apolyisobutene functionalized by silyl groups.

Suitable hydrosilylation catalysts include for example transition metalcatalysts, with the transition metal preferably being selected from Pt,Pd, Rh, Ru and Ir. Suitable platinum catalysts include for exampleplatinum in finely divided form (platinum black), platinum chloride andplatinum complexes such as hexachloroplatinic acid. Suitable rhodiumcatalysts are for example (RhCl(P(C₆H₅)₃)₃) and RhCl₃. RuCl₃ and IrCl₃are also suitable.

Suitable catalysts further include Lewis acids such as AlCl₃ or TiCl₄and also peroxides. It may be preferable to use combinations or mixturesof the aforementioned catalysts.

Suitable silanes are for example halogenated silanes, such astrichlorosilane, methyldichlorosilane, dimethylchlorosilane andtrimethylsiloxydichlorosilane; alkoxysilanes, such as trimethoxysilane,trimethoxysilane, methyldimethoxysilane, phenyldimethoxysilane,1,3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane and alsoacyloxysilanes.

The reaction temperature in the silylation is preferably in the rangefrom 0 to 120° C. and more preferably in the range from 40 to 100° C.The reaction is typically carried out under atmospheric pressure, but itcan also be carried out at superatmospheric pressures, for example inthe range of about 1.5-20 bar, or reduced pressures, for example in therange from 200 to 600 mbar.

The reaction can be carried out without solvent or in the presence of asuitable solvent. Examples of preferred solvents are toluene,tetrahydrofuran and chloroform.

vii) Addition of Hydrogen Halide or Halogen

The reactive polyisobutene may be functionalized by reaction withhydrogen halide or halogen to obtain a polyisobutene functionalized byhalogen groups.

Suitable reaction conditions for the hydro-halo addition are describedin J. March, Advanced Organic Chemistry, 4th edition, John Wiley & Sons,pages 758-759, incorporated herein by reference. Hydrogen halidessuitable for the addition reaction are in principle HF, HCl, HBr and HI.The addition of HI, HBr and HF can generally be carried out at roomtemperature, whereas the addition of HCl is generally carried out usingelevated temperatures.

The addition of hydrogen halides can in principle be carried out in theabsence or in the presence of initiators or of electromagneticradiation. Addition in the absence of initiators, specificallyperoxides, generally gives the Markovnikov addition products. Whenperoxides are present, the addition of HBr generally leads toanti-Markovnikov products.

The halogenation of double bonds is described in J. March, AdvancedOrganic Chemistry, 4th edition, John Wiley & Sons, pages 812-814,incorporated by reference. Cl, Br and I can be added using the freehalogens. The use of interhalogen compounds is known for obtainingcompounds having mixed halogenation. Fluorine is generally added usingfluorine-containing compounds, such as CoF₃, XeF₂ and mixtures of PbO₂and SF₄. Bromine generally adds to double bonds at room temperature ingood yields. Chlorine can be added not only via the free halogen butalso from chlorine-containing reagents, such as SO₂Cl₂, PCl₅, etc.

When the halogenation is carried out using chlorine or bromine in thepresence of electromagnetic radiation, the products obtained aresubstantially the products of free-radical substitution to the polymerchain and only to a minor extent, if at all, addition products to theterminal double bond.

viii) Hydroboration

The reactive polyisobutene may be functionalized by reaction with aborane (optionally generated in situ) to obtain a hydroxylatedpolyisobutene.

Suitable hydroboration methods are described in J. March, AdvancedOrganic Chemistry, 4th edition, John Wiley & Sons, pages 783-789,incorporated herein by reference. Examples of suitable hydroborationreagents are diborane, which is generally generated in situ by reactionof sodium borohydride with BF₃ etherate, diisamylborane(bis[3-methylbut-2-yl]borane), 1,1,2-trimethylpropylborane,9-borabicyclo[3.3.1]nonane, diisocamphylborane (which are obtainable byhydroboration of the corresponding alkenes with diborane),chloroborane-dimethyl sulfide, alkyldichloroboranes or H₃B—N(C₂H₅)₂.

The hydroboration is typically carried out in a solvent. Examples ofsuitable solvents for the hydroboration are acyclic ethers such asdiethyl ether, methyl tert-butyl ether, dimethoxyethane, diethyleneglycol dimethyl ether, triethylene glycol dimethyl ether, cyclic etherssuch as tetrahydrofuran or dioxane and also hydrocarbons such as hexaneor toluene or mixtures thereof. The reaction temperature is generallydetermined by the reactivity of the hydroborating agent and is normallyin the range from the melting point to the boiling point of the reactionmixture and preferably in the range from 0° C. to 60° C.

The hydroborating agent is typically used in excess, based on thealkene. The boron atom preferentially adds to the less substituted andhence sterically less hindered carbon atom.

The alkylboranes formed are usually not isolated, but are converteddirectly into products of value by subsequent reaction. A very importantreaction of the alkylboranes is the reaction with alkaline hydrogenperoxide to give an alcohol which preferably corresponds formally to theanti-Markovnikov hydration of the alkene. Furthermore, the alkylboranesobtained can be subjected to a reaction with bromine in the presence ofhydroxide ions to give the bromide.

ix) Reaction with an SO₃ Source

The reactive polyisobutene may further be functionalized with an SO₃source to obtain a polyisobutene having terminal sulfonic acid groups.

The sulfo-functionalized polyisobutenes can be formed by reaction of thereactive polyisobutenes with an SO₃ source. Suitable SO₃ sources includea mixture of sulfur trioxide and air, sulfur trioxide hydrates, sulfurtrioxide amine complexes, sulfur trioxide ether complexes, sulfurtrioxide phosphate complexes, acetyl sulfate, a mixture of sulfurtrioxide and acetic acid, sulfamic acid, alkyl sulfates orchlorosulfonic acids. The reaction can be carried out in the absence ofa solvent or in an arbitrary inert anhydrous solvent. Suitable reactiontemperatures are in the range from −30° C. to +200° C. and depend on thesulfonating reagent used. For example, a sulfonation with acetyl sulfateat low temperatures and elevated temperatures should be avoided, or theproduct may decompose. The sulfonating reagent is generally used in amolar ratio in the range from 1:1 to 2:1 to polyisobutene. Preference isgiven to using acetyl sulfate or a mixture of sulfuric acid and aceticanhydride, in which case acetyl sulfate is formed in situ, and thesulfo-functionalized polyisobutene is formed directly. Others of thesulfonating reagents mentioned, for example the mixture of sulfurtrioxide and oxygen, may initially form a sultone intermediate, whichhas to be hydrolyzed to the desired sulfonic acid. A process forpreparing sulfo-functionalized polyisobutenes is disclosed for examplein WO 01/70830.

x) Functionalization with Amino Groups

The reactive polyisobutene may be functionalized by reaction withnitrogen oxides and subsequently hydrogenated to obtain polyisobuteneshaving terminal amino groups.

Suitable nitrogen oxides include for example NO, NO₂, N₂O₃, N₂O₄,mixtures of these nitrogen oxides with each other and mixtures of thesenitrogen oxides with oxygen. Particular preference is given to mixturesof NO or NO₂ with oxygen. The nitrogen oxides may further additionallycontain inert gases, for example nitrogen. The reaction of thepolyisobutenes with the nitrogen oxides is generally carried out at from−30 to +150° C. in an inert organic solvent. The products obtained aresubsequently hydrogenated, preferably by catalytic hydrogenation withhydrogen in the presence of hydrogenation catalysts. The hydrogenationis generally carried out at from 20 to 250° C., depending on thereducing system used. The hydrogenation pressure in the catalytichydrogenation is generally in the range from 1 bar to 300 bar. A processfor preparing amino-terminated addition polymers is described forexample in WO 97/03946.

Fibers, Films, Moldings Formed from the Polymer Composition of thePresent Invention

The polymer compositions of the present invention can be furtherprocessed in any desired fashion. The present invention thereforefurther provides fibers, films and moldings formed from the polymercomposition of the present invention.

The term “fibers” as used herein refers to fibers of all lengths anddiameters. The term “fibers” as used herein likewise comprehends“filaments” and “staple fibers”. The term “fibers” further comprehendsnot only the individual fibers themselves but yarns, wovens, knits,knotted carpets or nonwoven formed from these fibers. Processes forproducing fibers and yarns, wovens, knits, carpets or nonwoven formedtherefrom and composed of the polymer compositions according to thepresent invention are known to one skilled in the art.

The term “films” as used herein comprehends plastic films and sheets ofany desired thickness and also their processing products. Suitableprocesses for producing and processing films are known to one skilled inthe art.

By “moldings” are meant any articles, parts, semi-finished products,plates and blown shapes which are producible from the polymercompositions according to the present invention by extrusion molding,injection molding, blow molding and rotor molding with or withoutcalendering.

Production of the Polymer Compositions

The present invention further provides a process for producing thepolymer compositions of the present invention, which comprisescontacting the hydrophobic polymer, especially the polyolefin, or thestarting materials used for preparing the hydrophobic polymer,especially the polyolefin, with at least one polyisobutene modified byterminal polar groups.

Monomers suitable for preparing the hydrophobic polymer, especially thepolyolefin, were mentioned above. Processes for preparing hydrophobicpolymers and especially polyolefins are known to one skilled in the art.

The polymer compositions and the fibers, films and moldings formed fromthe polymer compositions of the present invention can be produced invarious ways:

-   -   a) Preparation of the hydrophobic polymers and especially of the        polyolefins in the presence of the modified polyisobutenes used        according to the present invention

When the hydrophobic polymers and especially the polyolefins areprepared in the presence of the modified polyisobutenes used accordingto the present invention, the polyisobutenes are generally notincorporated as a copolymer into the hydrophobic polymer and especiallythe polyolefin, but are merely present in finely divided form in thepolymer matrix. However, it is also conceivable for suitably modifiedpolyisobutenes to be firmly incorporated as a copolymer into thehydrophobic polymer and preferably into the polyolefin. In any case, themodified polyisobutenes are not merely applied to the surface of thepolyolefin, but become firmly attached in the bulk of the polymermaterial. Thus, substances used for further modification, for exampledyes, can be attached not just to the surface of the polyisobutenes butalso to the bulk of the polymer material. This provides for example dyedpolymer compositions which can be further processed into the fibers,films and moldings mentioned. The dyes are firmly attached in thepolymer compositions, so that lixiviation of the dyes is substantiallyavoided. Suitable methods are known to one skilled in the art.

-   -   b) Addition of modified polyisobutenes in the course of the        processing of the hydrophobic polymers (especially polyolefins)        used

It is likewise possible to add the modified polyisobutenes usedaccording to the present invention in the course of the processing ofthe hydrophobic polymers, especially polyolefins, into fibers, films andmoldings, for example in the course of the extrusion molding, injectionmolding, blow molding or rotor molding of the hydrophobic polymers,especially polyolefins. In this version of the process, the polymercompositions according to the present invention are mixtures between thehydrophobic polymers (especially polyolefins) used and the modifiedpolyisobutenes. What is achieved in this case too is not merely amodification of the surface of the hydrophobic polymers, especiallypolyolefins, but a dispersion of the modified polyisobutene within thehydrophobic polymers, especially polyolefins. Suitable methods are knownto one skilled in the art.

The present invention accordingly further provides a process forproducing the moldings, films and fibers which are according to thepresent invention, which comprises contacting the modified polyisobutenewith the hydrophobic polymer, especially polyolefin, during theprocessing into moldings, films and fibers.

-   -   c) Applying the modified polyisobutenes

It is finally possible to produce fibers, films and moldings fromhydrophobic polymers, especially polyolefins, by processes known to oneskilled in the art and only then to apply the modified polyisobutenesused according to the present invention by processes known to oneskilled in the art. In this case, it is merely the surface of thefibers, films and moldings which is modified by means of the modifiedpolyisobutenes. Thus, for example in the case of a dyeing of the thusmodified hydrophilic polymers, especially polyolefins, it is merely thesurface of the fibers, films and moldings that is dyed.

The present invention accordingly further provides a process forproducing the fibers, films and moldings which are according to thepresent invention, which comprises applying the modified polyisobuteneto the fibers, films and moldings formed from polyolefin.

While the modified polyisobutenes are generally contacted with thehydrophobic polymers, especially polyolefins, without a solvent inversions a) and b), the application of the modified polyisobutenes usedaccording to the present invention in version c) is preferably effectedfrom a solution, emulsion or dispersion of the modified polyisobutenesused according to the present invention in solvents, preferably fromaqueous systems, by application in liquid form, by spraying, as a spray,aerosol or in the vapor phase.

The polymer compositions according to the present invention generallycomprise from 85% to 99.9% by weight, preferably from 90% to 99.8% byweight and more preferably from 95% to 99.5% by weight of thehydrophobic polymer, especially polyolefin, and generally from 0.1% to15% by weight, preferably from 0.2% to 10% by weight and more preferablyfrom 0.5% to 5% by weight of the polyisobutene derivative used accordingto the present invention. The polymer compositions according to thepresent invention may further optionally comprise further componentssuch as other polymers which are miscible with hydrophobic polymers,especially polyolefins and which are added for example to improve thetechnological properties, and processing assistants, stabilizers such asUV absorbers, antioxidants and free-radical scavengers (for example HALSamines), antistats, flame retardants, nucleating agents, fillers, aslong as they do not form undesirable compounds with the substancesaccording to the present invention. Details are known to one skilled inthe art and can be read up for example in the polyolefins chapter of“Ullmanns Encyclopedia (of Technical Chemistry), 6^(th) Edition, 2000Electronic Release” and the references cited therein.

The polymer compositions according to the present invention remedy thedisadvantages of the unmodified hydrophobic polymers, especiallypolyolefins. The polymer compositions according to the present inventionand fibers, films and moldings formed from the polymer compositionsaccording to the present invention are dyeable from aqueous baths,directly coatable or printable and adherable to other materials. Thusthe polymer compositions according to the present invention are veryuseful for industrial and automotive textiles and apparel fibers,specifically in the sports and outdoor apparel sector, and also asdyeable and printable fibers for producing textile sheet materials, suchas carpets or nonwovens, and for parts and semi-finished products forthe automotive, building construction and household sectors, as housingsfor a very wide variety of instruments, for packaging, industrialapplications.

Dyeing of the Polymer Composition According to the Present Invention

The present invention accordingly further provides a process for dyeingthe polymer composition according to the present invention or thefibers, films and moldings according to the present invention, whichcomprises contacting a liquor containing at least one dye with thepolymer composition or the fibers, films and moldings.

The composition of the liquor is dependent on the dyeing method used andon the dye used. The choice of suitable dyes depends on the requirementswith regard for example to in-service fastnesses, depth of shade andbrilliance of the dyeing, whereby the choice of functionalization of themodified polyisobutene used according to the present invention isdetermined. Good adhesion of the dye in the polymer composition or thefibers, films and moldings formed from the polymer composition isobtained whenever the functional groups of the dyes used arecomplementary to the terminal polar groups of the polyisobutenes used.

By “complementary group” as used herein is meant a pair of functionalgroups which are able to react with each other by forming a covalentbond, salt formation through electrostatic interaction, hydrogen bondingor van der Waals interactions.

Useful dyes include in principle all known dyes selected from cationicdyes, anionic dyes, mordant dyes, direct or substantive dyes, dispersedyes, ingrain dyes, vat dyes, metalized dyes, reactive dyes, sulfur dyesdyes. The use of the various dyes is dependent inter alia on themodified polyisobutene used for modifying the polyolefins.

There now follows a recitation of the modified polyisobutenes obtainedafter a functionalization as per one of the steps i) to x) and of thedyes suitable for dyeing the polymer compositions containing thesemodified polyisobutenes:

i) Alkylation of Aromatic Hydroxy Compounds

The alkylation of aromatic hydroxy compounds and of phenols inparticular yields polyisobutenylphenols. Polyisobutenylphenols aremodified polyisobutenes which are able to interact with disperse dyes,direct dyes, vat dyes, metalized dyes, reactive dyes, sulfur dyes andsubstantive and also (in the event of a substitution with anionic orcationic functional groups) with cationic and anionic, as the case maybe, dyes.

A further functionalization of the polyisobutenylphenols obtained instep i) by a Mannich reaction with at least one aldehyde and at leastone amine yields a polyisobutene-alkylated and additionalamino-alkylated compound. These modified polyisobutenes are able tointeract with anionic dyes because of the positive charge on the aminogroup, which charge may be permanent as a consequence of quaternizationof the amino group or temporary in the case of acidic dyeing conditions.

ii) Epoxidation

Epoxidation of the polyisobutenes gives an epoxidized polyisobutene.This is able to interact with mordant dyes, direct dyes, disperse dyes,ingrain dyes, vat dyes, metalized dyes, reactive dyes, sulfur dyes andsubstantive dyes.

The epoxidized polyisobutenes obtained in step ii) may be furtherfunctionalized by reaction with ammonia to obtain polyisobutylaminoalcohols. These are able, under suitable conditions, to preferentiallyinteract with anionic dyes.

iii) Ene Reaction

An ene reaction yields in particular polyisobutenes modified by succinicanhydride groups. The anhydride groups of the substances according tothe present invention can be hydrolyzed to dicarboxylic acid radicalsprior to processing or at least partially react during the processingaccording to the present invention to form dicarboxylic acid radicals.The anhydride and dicarboxylic acid groups are able to preferentiallyinteract with cationic dyes.

The polyisobutenes modified by succinic anhydride groups can react withmaleic anhydride for a second time to form a product having two succinicanhydride groups at the chain end (known as PIBBSA). PIBBSA is in turnable to preferentially interact with cationic dyes.

iv) Hydroformylation

Hydroformylation is a way of obtaining polyisobutenes having alcoholgroups. These can interact with mordant dyes, direct or substantivedyes, disperse dyes, ingrain dyes, vat dyes, metalized dyes, reactivedyes, sulfur dyes and.

Further functionalization of the modified polyisobutenes obtained by thereaction as per iv) makes it possible to obtain various functionalizedisobutenes:

A) Oxocarboxylic Acids

Oxidation of the hydroformylated polyisobutenes is a way to obtaincarboxyl-functionalized polyisobutenes. These are preferentially able tointeract with cationic dyes.

B) Oxo Alcohols

Reaction with hydrogen in the presence of a hydrogenation catalystconverts the hydroformylated polyisobutenes into alcohol-functionalizedpolyisobutenes, if these are not already directly obtained in the courseof the hydroformylation. These are able to interact with mordant dyes,direct dyes, disperse dyes, ingrain dyes, vat dyes, metalized dyes,reactive dyes, sulfur dyes and substantive dyes. The polyisobutenesfunctionalized by alcohol groups may additionally be alkoxylated withalkylene oxides, preferably ethylene oxide. The modified polyisobutenesobtained are able to interact with mordant dyes, direct or substantivedyes, disperse dyes, ingrain dyes, vat dyes, metalized dyes, reactivedyes, sulfur dyes and cationic dyes.

C) Amine Synthesis

The hydroformylated isobutenes obtained in step iv) can be reacted withhydrogen and ammonia or a primary or secondary amine in the presence ofan amination catalyst to obtain polyisobutenes functionalized by aminegroups. These polyisobutenes are able to preferentially interact withanionic dyes.

V) Addition of Hydrogen Sulfide or Thiols

Reaction of polyisobutene with hydrogen sulfide or a thiol is a way toobtain thio-functionalized polyisobutenes. These are able to interactwith mordant dyes, direct dyes, disperse dyes, ingrain dyes, vat dyes,metalized dyes, reactive dyes, sulfur dyes, substantive and cationicdyes.

vi) Silylation

Functionalization of the polyisobutenes with silanes givessilyl-functionalized polyisobutenes. These are able to interact withmordant dyes, direct dyes, disperse dyes, ingrain dyes, vat dyes,metalized dyes, reactive dyes, sulfur dyes, substantive and cationicdyes.

vii) Addition of Hydrogen Halide or Halogen

Functionalization of polyisobutene with halogenic hydrogen or a halogenis a way to obtain polyisobutenes functionalized by halogen groups.These polyisobutenes are able to interact with disperse dyes, directdyes and sulfur dyes.

viii) Hydroboration

Hydroboration of the polyisobutenes is a way to obtain alcohols. Theseare able to interact with mordant dyes, direct dyes, disperse dyes,ingrain dyes, vat dyes, metalized dyes, reactive dyes, sulfur dyes andsubstantive dyes.

ix) Reaction with an SO₃ Source

Reaction with compounds which transfer SO₃ groups is a way to obtainpolyisobutenes having terminal sulfonic acid groups. These are able topreferentially interact with cationic dyes.

x) Reaction with Nitrogen Oxides and Subsequent Hydrogenation

Reaction with nitrogen oxides and subsequent hydrogenation of thepolyisobutenes makes polyisobutenes having terminal amino groupsavailable. These are able to preferentially interact with anionic dyes.

The foregoing enumeration represents only a small selection from thenumerous possibilities for dyeing the polymer compositions according tothe present invention. Owing to the numerous possible ways offunctionalizing the modified polyisobutenes used according to thepresent invention it is possible to obtain polyolefin compositions whichcan interact with, ie be dyed by, numerous different dyes. It is thuspossible to arrive at an optimum combination of polymer composition,comprising a modified polyisobutene, and a dye for any application. Thepolymer compositions according to the present invention hence are verywidely useable.

To obtain high in-service fastnesses, dyeing with ionic dyes may bepreferable. When it is necessary to dye the polyolefin fibers in a blendwith other fiber varieties, such as natural fibers (for example cottonor wool) or synthetic fibers (such as polyester or polyamide), it may bepreferable to dye both fibers with the same type of dye, for example todye a cotton-polypropylene blend with direct dyes.

Suitable liquors for dyeing the polymer compositions of the presentinvention or the fibers, films and moldings of the present invention andalso suitable dyeing methods and suitable dyes for the various dyeingmethods are known to one skilled in the art. The dyeings can be effectedin different forms of makeup (as yarn, tow, woven fabric, knitted fabricor nonwoven) batchwise in customary dyeing machines such as winch becks,yarn dyeing machines, beam dyeing machines and jets or continuously bynip-padding, face-padding, spraying or foam application processes usingsuitable drying and fixing means.

The present invention further provides dyed polymer compositionscomprising:

-   -   a) at least one hydrophobic polymer and especially a polyolefin,    -   b) at least one polyisobutene which is modified by terminal        polar groups and is obtainable by functionalization of reactive        polyisobutene having a number average molecular weight M_(n)        from 150 to 50 000, and    -   c) at least one dye.

Suitable polyolefins, polyisobutenes and dyes are as mentioned above.

Particular preference is given to combinations of anionically andcationically modified polyisobutenes and the oppositely charged dyes.

These polymer compositions combine the excellent properties of thepolyolefins with a good dyeability, which is achieved because of themodified polyisobutenes used. The polymer compositions are notable forthe dye being firmly fixed in the polymer composition and beingresistant to lixiviation. Furthermore, the polymer compositions can bedyed with the processes known for the dyes which are suitable in eachcase and assistants for dyeing polymer compositions.

The present invention further provides fibers, films and moldings formedfrom the dyed polymer composition of the present invention.

The dyed polymer compositions of the present invention and the dyedfibers, films and moldings of the present invention are obtainable invarious ways. This is dependent inter alia on when the modifiedpolyisobutene is added to the hydrophobic polymer, especiallypolyolefin. As explained above, this is possible directly in the courseof the preparation of the hydrophobic polymer, especially polyolefin, inthe course of its further processing or following its processing. Thedye is preferably incorporated in the polymer composition followingprocessing or applied to the fibers, films and moldings obtained.However, it is also possible for the polymer composition itself to bedyed directly.

The present invention further provides for the use of at least onepolyisobutene modified by terminal polar groups which is obtainable byfunctionalization of reactive polyisobutene having a number averagemolecular weight M_(n) from 150 to 50 000 for hydrophilicizinghydrophobic polymers, especially polyolefins.

Preferred modified polyisobutenes and also preferred hydrophobicpolymers, especially polyolefins, are known to one skilled in the art.The term “hydrophilicization” is likewise known to one skilled in theart.

The examples which follow illustrate the invention.

EXAMPLES

Extrusion Tests

Polypropylene: Metocene® X50248 (from Basell). Metocene® X50248 is ahomopolypropylene (metallocene catalysis). It is specifically useful fornonwovens, staple fibers and filaments.

Product data of homopolypropylene without additions:

Properties Method Unit Values Melt flow rate ISO 1133 g/10 min 18Tensile strength ISO 527-2 MPa 32 Elongation ISO 527-2 % 9 Elongation atbreak ISO 527-2 % >50 Melting point (DSC) ISO 3146 ° C. 146 Temperatureof deflection ISO 75-2 ° C. 88 under load Density ISO 1183 G/cm³ 0.91

In each case, 5% by weight of the hereinbelow specified polyisobutenesmodified by terminal polar groups was added to the polypropylene chips.

The tests were carried out in a twin-screw extruder at a housingtemperature of 180° C. and 200 rpm. Die outputs are 1×4 mm.

The throughput is 5 kg/h and the polyisobutene additive modified bypolar groups is added at a throughput of 250 g/h. The metering pump runsat 100-200 g/h.

Spinning:

The stretch ratio is 3:1 and the linear density is 17 dtex. Spinningtakes place at 200° C./230° C.

Production of Textile Sheet Materials:

All the extruded polymer fibers additized with the substances of thepresent invention were processed into woven or knitted fabrics whichwere dyed by the hereinbelow specified methods. The use of textile sheetmaterials ensures the evaluation of the levelness of textile finishingoperations and, for example, of the hand.

Test Plates:

Each chip product obtained after extrusion was used to press plates(about 160×160×2 mm; weight about 46 g; pressing time 4 min at 220° C.,1 min each at 50, 100, 150 and 200 bar).

The plates obtained were used for dyeing tests:

Dyeings:

The dyeings were carried out by heating the knits produced frompolypropylene additized with the substances according to the presentinvention in demineralized water in the presence of the stated dyes atthe stated pH in an AHIBA dyeing machine from initially 110° C. to 130°C. over 20 minutes and leaving them at 130° C. for 2 hours. The liquorratio, ie the ratio of the volume of the treatment bath in liters to themass of the dry polypropylene knit in kilograms, was 50:1. After dyeing,the dyeings were cooled to about 80° C., removed, rinsed cold and driedat 100° C.

The depth of shade achieved was evaluated. A comparative knit formedfrom nonadditized polypropylene and co-treated in each case exhibited nodyeing whatsoever.

Cationic Dyeing:

1.1% of Basacryl Red X-BL 300%

Polyisobutene Used According to the Present Invention:

-   -   a) polyisobutene succinic anhydride obtained from polyisobutene        of molar mass 550 by ene reaction with maleic anhydride and        hydrolyzed with water to the dicarboxylic acid;    -   b) polyisobutenesulfonic acid prepared similarly to WO 01/70830        A2 from polyisobutene of molar mass 550 or 1000 by sulfonation;    -   c) polyisobutene succinic anhydride obtained from polyisobutene        of molar mass 550 by ene reaction with maleic anhydride and        reacted with polyglycol ether of molar mass 300 to the        corresponding monoester.

Liquor ratio=50:1 (Note. The long liquor ratios reported here were usedon account of the small substrate quantities and are not associated withthe substances used according to the present invention. The currentlycustomary, very short liquor ratios can be used on an industrial scale.)

pH 6, set with buffer solution

Anionic Dye:

2.5% of Telon Red FRL 200%

Polyisobutene Used According to the Present Invention:

-   -   d) polyisobutene Mannich TEPA prepared in accordance with or in        analogy with WO 01/25 293 and WO 01/25 294) from polyisobutene        of molar mass 1000 by alkylation with phenol and subsequent        Mannich reaction with formaldehyde and tetraethylenepentamine;    -   e) polyisobutene succinic anhydride obtained from polyisobutene        of molar mass 1000 by ene reaction with maleic anhydride and        reacted with tetraethylenepentamine to form the corresponding        succinimide.

Liquor ratio=50:1

pH 4.5, set with buffer solution

The dyeings obtained were even without a leveling agent level and deepin shade. In the case of PIBSA PEG monoester, the dyeings weredistinctly more light-colored. The hand of the knit fabrics was notharshened. The washfastness of the dyeings obtained was determined in ahigh-speed wash with 2 g/l of FEWA mild detergent, liquor ratio 200:1, 5minutes at 60° C. The evaluation criterion was whether the PP dyeingbecame lighter during the wash, ie whether there was dye bleed, andwhether adjacent fabric was stained.

All the substances according to the present invention gave satisfactorywashfastnesses.

Preparation of the Modified Polyisobutene Derivatives Used as per a) toe)

Re a)

-   -   Preparation of PIB succinic anhydride similarly to DE-A 4 319        672, EP-A 0 156 310 or H. Mach and P. Rath in “Lubrication        Science II” (1999), p. 175-185. Hydrolysis of PIBSA 550:    -   A 1 l three-neck flask is charged with 50 ml of water and 50 ml        of tetrahydrofuran at room temperature. A solution of 275 g of        PIBSA (85% of α-olefin fractions, Mn=550; DP=1.65; based on        polyisobutene) in 150 ml of tetrahydrofuran was added dropwise.        This is followed by stirring at that temperature for 30 min.        Thereafter, the solvent is completely stripped off under reduced        pressure. To remove the remaining water, it is entrained out as        an azeotrope with toluene. This is followed by drying over        Na₂SO₄.    -   IR spectrum: OH vibration at 3454 cm⁻¹, C═O stretch vibration of        succinic acid structure at 1710 cm⁻¹, C═C stretch vibration 1636        cm⁻¹. In addition there are vibrations of the PIB structure at        2951, 2896, 1473, 1389, 1365 and 1236 cm⁻¹.        Re b)    -   Preparation similarly to WO 01/70830 A2        Re c)    -   Reaction of polyisobutene 550 with polyglycol ether 300 to form        the corresponding monoester.    -   A 2 l three-neck flask is charged with 347 g of PIBSA (85% of        α-olefin fractions, M_(n)=550; DP=1.65; based on polyisobutene),        and the contents are heated to 90° C. 300 g of polyethylene        glycol (Pluriol® E 300, M_(n)=300) which had been heated to        80° C. are added dropwise. On completion of the addition the        batch is stirred at 90° C. for 3 hours and then cooled down.    -   IR spectrum: OH vibration at 3298 cm⁻¹, C═O stretch vibration of        succinic monoester structure at 1734 cm⁻¹, C═C stretch vibration        1639 cm⁻¹, C—O—C ether vibration at 1110 cm⁻¹. In addition there        are vibrations of the PIB structure at 2953, 2893, 1471, 1389,        1366 and 1233 cm⁻¹.    -   Reactions with variable PIBSA radicals (PIB fraction M_(n)=200,        550, 1000, 2300, etc) and polyethylene glycol radicals        (M_(n)=300, 600, 1500, 4000, 6000, 9000, 12000, etc) were        carried out in similar fashion having regard to the starting        weights.        Re d)    -   Preparation similarly to WO 01/25 293 and WO 01/25 294        Re f)    -   PIBSA 1000 with tetraethylpentamine (PIBSA imide)    -   A 2 l four-neck flask is charged with 582 g of PIBSA (85% of        α-olefin fractions, M_(n)=1000; DP=1.70; based on polyisobutene)        and 63.8 g of ethylhexanol under an inert gas atmosphere        (nitrogen). This is followed by heating to 140° C. before 99.4 g        of tetraethylpentamine are added dropwise. On completion of the        addition, the temperature is raised to 160° C. and maintained        for 3 h. During the reaction, volatiles distill over to some        extent. For completion, the pressure is reduced to 500 mbar for        30 min toward the end of the reaction. This is followed by        cooling to room temperature. IR spectrum: NH vibration at 3295,        1652 cm⁻¹, C═O stretch vibration of succinimide structure at        1769, 1698 cm⁻¹. In addition there are vibrations of the PIB        structure at 2953, 1465, 1396, 1365 and 1238 cm⁻¹.

1. A polymer composition comprising a) at least one hydrophobic polymerin the form of a homo- or copolymer of propylene or in the form of ahomo- or copolymer of ethylene, and b) at least one polyisobutene whichis modified by terminal polar groups and is obtained byfunctionalization of reactive polyisobutene having a number averagemolecular weight M_(n) from 150 to 50,000.
 2. A polymer composition asclaimed in claim 1, wherein said reactive polyisobutene has a terminaldouble bond content of not less than 50 mol %.
 3. A polymer compositionas claimed in claim 1, wherein said functionalization of saidpolyisobutene is accomplished in one or more stages and is selected fromi) reaction with aromatic hydroxy compounds in the presence of analkylation catalyst to obtain polyisobutene-alkylated aromatic hydroxycompounds; ii) reaction of said polyisobutene with a peroxy compound toobtain an epoxidized polyisobutene; iii) reaction of said polyisobutenewith an alkene having an electrophilically substituted double bond (anenophile) in an ene reaction; iv) reaction of said polyisobutene withcarbon monoxide and hydrogen in the presence of a hydroformylationcatalyst to obtain a hydroformylated polyisobutene; v) reaction of saidpolyisobutene with hydrogen sulfide or a thiol to obtain athio-functionalized polyisobutene; vi) reaction of said polyisobutenewith halogen or a hydrogen halide to obtain a halogen-functionalizedpolyisobutene; vii) reaction of said polyisobutene with a borane andsubsequent oxidative cleavage to obtain a hydroxylated polyisobutene;viii) reaction of said polyisobutene with a silane in the presence of asilylation catalyst to obtain a silyl-functionalized polyisobutene; ix)reaction of said polyisobutene with an SO₃ source to obtainpolyisobutenes having terminal sulfonic acid groups; x) reaction of saidpolyisobutene with nitrogen oxides and subsequent hydrogenation toobtain polyisobutenes having terminal amino groups.
 4. A polymercomposition as claimed in claim 3, wherein said functionalization ofsaid polyisobutene is accomplished by reaction of said polyisobutenewith acetyl sulfate as the SO₃ source to obtain polyisobutenes havingterminal sulfonic acid groups.
 5. A fiber, film or molding formed from apolymer composition as claimed in claim
 1. 6. A process for producing apolymer composition as claimed in claim 1, which comprises contactingsaid hydrophobic polymer (component a) or the monomers used forpreparing said hydrophobic polymer with at least one polyisobutenemodified by terminal polar groups (component b).
 7. A process as claimedin claim 6, wherein said polyisobutene is used as a comonomer in thepreparation of said hydrophobic polymer.
 8. A process for producing amolding, film or fiber as claimed in claim 5, which comprises contactingat least one polyisobutene modified by terminal polar groups with saidhydrophobic polymer during the processing into a molding, film or fiber.9. A process for producing a fiber, film or molding as claimed in claim5, which comprises applying at least one polyisobutene modified byterminal polar groups onto said fiber, film or molding formed from saidhydrophobic polymer.
 10. A process for dyeing a polymer compositioncomprising a) at least one hydrophobic polymer in the form of a homo- orcopolymer of propylene or in the form of a homo- or copolymer ofethylene, and b) at least one polyisobutene which is modified byterminal polar groups and is obtained by functionalization of reactivepolyisobutene having a number average molecular weight M_(n) from 150 to50,000 or a fiber, film or molding formed from said polymer composition,which process comprises contacting said polymer composition or saidfiber, film or molding with a liquor containing at least one dye.
 11. Adyed polymer composition comprising (1) a polymer composition comprisinga) at least one hydrophobic polymer in the form of a homo- or copolymerof propylene or in the form of a homo- or copolymer of ethylene, and b)at least one polyisobutene which is modified by terminal polar groupsand is obtained by functionalization of reactive polyisobutene having anumber average molecular weight M_(n) from 150 to 50,000 and (2) atleast one dye.
 12. A fiber, film or molding formed from a dyed polymercomposition as claimed in claim
 11. 13. A method of hydrophilicizinghydrophobic polymers in the form of a homo- or copolymer of propylene orin the form of a homo- or copolymer of ethylene, comprising the step ofcontacting said hydrophobic polymers in the form of a homo- or copolymerof propylene or in the form of a homo- or copolymer of ethylene, with atleast one polylsobutene modified by terminal polar groups and isobtained by functionalization of reactive polyisobutene having a numberaverage molecular weight M_(n) from 150 to 50,000.